CN115779937B - Method for activating lattice oxygen on surface of perovskite oxide and application of method - Google Patents
Method for activating lattice oxygen on surface of perovskite oxide and application of method Download PDFInfo
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Abstract
The invention discloses a method for activating lattice oxygen on the surface of perovskite oxide and application thereof, relating to the technical field of waste gas treatment, comprising the steps of preparing a perovskite catalyst precursor doped with fluoride ions by a hydrothermal method, drying, and calcining for 2 hours at a certain temperature rising rate to obtain a final perovskite catalyst; the invention improves the lattice oxygen activity on the surface of perovskite through doping fluorine ions, shows excellent catalytic activity, is suitable for improving the catalytic performance of fluorine-doped perovskite metal oxides prepared by different methods, has simple and convenient treatment method, remarkably improves the catalytic combustion performance of the catalyst on VOCs, and has good heat resistance and stable performance.
Description
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a method for activating lattice oxygen on the surface of perovskite oxide and application thereof.
Background
In recent years, the type of environmental air pollution has gradually changed from soot type pollution to atmospheric haze and increased oxidizability (PM as lung-entering particulate matter, respectively 2.5 And ozone is a characteristic contaminant); considering the current atmospheric pollution condition, the pollution control of VOCs is carried out on the string.
Catalytic combustion is an economical and effective means for the treatment of VOCs exhaust gas. As a traditional organic waste gas treatment technology, a catalytic combustion method is one of the main technologies for VOCs treatment at present, wherein the development of high-efficiency low-cost catalytic materials is the key of popularization and application of the technology.
Perovskite-type oxide catalysts have been attracting attention because of their excellent heat resistance and structural stability, and the catalytic activity of the perovskite-type oxide catalysts reported so far often cannot meet the industrial application demands under low temperature conditions. Therefore, on the premise of maintaining excellent heat resistance and structural stability of the perovskite oxide material, improving the low-temperature catalytic oxidation performance of the perovskite oxide material is a key point that the perovskite oxide catalyst can meet the industrial application requirements.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a method for activating lattice oxygen on the surface of perovskite oxide and application thereof.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a method for activating lattice oxygen on the surface of perovskite oxide, which comprises the following steps:
s1, firstly, mixing lanthanum nitrate and nitrate, adding water for dissolution, adding a complexing agent after complete dissolution, finally adding fluoride salt, and stirring;
s2, carrying out hydrothermal reaction on the stirred solution in the step S1, and drying overnight after the hydrothermal reaction is finished to obtain a catalyst precursor;
s3, calcining the catalyst precursor obtained in the step S2.
Preferably, the nitrate is cobalt nitrate, ferric nitrate or manganese nitrate.
Preferably, the fluoride salt is cobalt fluoride, iron fluoride or manganese fluoride (wherein the sum of the amounts of metal ions in the nitrate salt and metal ion species in the fluoride salt is 0.005 mole).
Preferably, the complexing agent is one or more of tartaric acid, citric acid and EDTA.
Preferably, the fluoride salt is added in an amount of 10% to 50% of the amount of lanthanum nitrate species.
Preferably, the hydrothermal reaction temperature is 160-200 ℃ and the hydrothermal reaction time is 10 hours.
Preferably, the calcination temperature is 700-1000 ℃ and the calcination time is 2 hours.
Preferably, the temperature rising rate of the calcination process is 2-10 ℃/min.
A perovskite-type oxide catalyst, obtained according to the method, the perovskite-type oxide having ABO 3 Is a cube structure of (c).
The perovskite oxide catalyst is applied to catalyzing the combustion of VOCs.
The invention discloses the following technical effects:
the invention has simple reaction equipment, short reaction time and convenient operation of reaction; the raw materials for reaction are easy to obtain, the raw materials and the reaction cost are low, and the large-scale production is facilitated; in the whole reaction process, no toxic or harmful substances are used or generated, and the clean production requirement is completely met; the invention improves the lattice oxygen activity on the surface of the perovskite oxide through doping fluorine ions, shows excellent catalytic activity, is suitable for improving the catalytic performance of the fluorine-doped perovskite oxide prepared by different methods, has simple and convenient treatment method, remarkably improves the catalytic combustion performance of the catalyst on VOCs (particularly toluene), and has good heat resistance and stable performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows LaMnO before and after doping with fluorine ions in the embodiment of the invention 3 A catalytic performance comparison chart;
FIG. 2 shows LaCoO before and after doping with fluoride ions in an embodiment of the invention 3 A catalytic performance comparison chart;
FIG. 3 shows LaFeO before and after doping with fluoride ion in the embodiment of the invention 3 Catalytic performance comparison of (2);
FIG. 4 is a comparative example chloride and bromide doped LaCoO of the present invention 3 Catalytic performance diagram;
FIG. 5 is a 2.0mmolF doped LaCoO prepared in example 6 3 And the performance stability of the catalyst for degrading toluene is shown in the figure.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
According to a preferred embodiment of the invention, a method for activating lattice oxygen on the surface of a perovskite oxide comprises the following specific steps of preparing a perovskite catalyst precursor doped with fluorine ions through a hydrothermal method and preparing the perovskite catalyst through heat treatment:
s1, firstly, adding 0.005mol of lanthanum nitrate and a certain amount of nitrate into a beaker, wherein the nitrate is preferably cobalt nitrate, ferric nitrate or manganese nitrate; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent after complete dissolution, and finally adding a certain amount of corresponding fluoride salt, wherein the fluoride salt is cobalt fluoride, ferric fluoride or manganese fluoride (the sum of the amounts of metal ions in nitrate and metal ion substances in fluoride salt is 0.005 mol), and stirring for 6h;
specifically, by doping fluorine ions, the strong electron-withdrawing effect of the fluorine ions is utilized to weaken the strong bond between transition metal ions and oxygen ions in perovskite and promote the surface lattice oxygen activation so as to improve the catalytic combustion performance of the catalyst;
s2, placing the solution in the beaker after stirring for 6 hours in the S1 into a reaction kettle for hydrothermal reaction for 10 hours, and drying a sample in the reaction kettle at 80 ℃ overnight after the hydrothermal reaction for 10 hours to obtain a catalyst precursor;
s3, placing the catalyst precursor obtained in the S2 in a muffle furnace, and calcining for 2 hours at a certain temperature rising rate to obtain a perovskite catalyst;
preferably, the sample after complete drying in S2 is ground to a powder and placed in a muffle furnace.
The invention has simple reaction equipment, short reaction time and convenient operation of reaction; the raw materials for reaction are easy to obtain, the raw materials and the reaction cost are low, and the large-scale production is facilitated; in the whole reaction process, no toxic or harmful substances are used or generated, and the clean production requirement is completely met; the invention improves the lattice oxygen activity on the surface of the perovskite oxide through doping fluorine ions, shows excellent catalytic activity, is suitable for improving the catalytic performance of the fluorine-doped perovskite oxide prepared by different methods, has simple and convenient treatment method, remarkably improves the catalytic combustion performance of the catalyst on VOCs, and has good heat resistance and stable structure.
As a preferred embodiment of the invention, it may also have the following additional technical features:
in an embodiment of the present invention, the fluoride salt added in step S1 is 10% -50% of the amount of lanthanum nitrate species.
In an embodiment of the present invention, the complexing agent in step S1 is one or more of tartaric acid, citric acid and EDTA (ethylenediamine tetraacetic acid).
In an embodiment of the invention, the temperature of the hydrothermal reaction in step S2 is 160-200 ℃.
In the embodiment of the invention, the temperature rising rate in the step S3 is 2-10 ℃/min.
In an embodiment of the invention, the calcination temperature of the catalyst precursor in step S3 is 700-1000 ℃.
In an embodiment of the present invention, the perovskite catalyst has an ABO 3 Is a cube structure of (c).
The invention relates to a mass airspeed regulatorThe standard volumetric flow rate of reactant gas into the reaction system per hour is defined as divided by the mass of catalyst. Expressed in WHSV, unit mL.g -1 ·h -1 。
The toluene conversion in the present invention is defined as the volume percent of toluene that enters the reactor that is converted, i.e., the volume percent difference between the toluene in the inlet and outlet gases relative to the volume percent of toluene in the inlet gas in percent.
Example 1
Firstly, adding 0.005mol of lanthanum nitrate and 0.004mol of manganese nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent citric acid after complete dissolution, adding 1.0mmol of manganese fluoride, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 170 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 1.0mmol of fluorine ion doped LaMnO under the conditions of heating rate of 2 ℃/min and calcining at 900 ℃ for 2h 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaMnO 3 -1.0mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 2
Firstly, adding 0.005mol of lanthanum nitrate and 0.0035mol of manganese nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent tartaric acid after complete dissolution, adding 1.5mmol of manganese fluoride, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 180 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 1.5mmol of fluorine ion doped LaMnO under the conditions of heating rate of 2 ℃/min and calcining at 800 ℃ for 2h 3 LaMnO is added with 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaMnO 3 -1.5mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalystThe catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL/min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 3
Firstly, adding 0.005mol of lanthanum nitrate and 0.003mol of manganese nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent citric acid and EDTA (0.02 mol each) after complete dissolution, adding 2.0mmol of manganese fluoride, stirring for 6h, performing hydrothermal reaction at 160 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 2.0mmol of fluorine ion doped LaMnO under the conditions of heating rate of 2 ℃/min and calcining at 700 ℃ for 2h 3 LaMnO is added with 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaMnO 3 -2.0mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 。WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 4
Firstly, adding 0.005mol of lanthanum nitrate and 0.004mol of cobalt nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent EDTA after complete dissolution, adding 1.0mmol of cobalt fluoride, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 170 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and calcining at 900 ℃ for 2h at a heating rate of 5 ℃/min to prepare 1.0mmol of fluorine ion doped LaCoO 3 . LaCoO is carried out 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaCoO 3 -1.0mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 5
Firstly, adding 0.005mol of lanthanum nitrate and 0.0035mol of cobalt nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent citric acid after complete dissolution, adding 1.5mmol of cobalt fluoride, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 180 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 1.5mmol of fluorine ion doped LaCoO under the conditions of heating rate of 5 ℃/min and calcining at 800 ℃ for 2h 3 . LaCoO is carried out 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaCoO 3 -1.5mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 6
Firstly, adding 0.005mol of lanthanum nitrate and 0.003mol of cobalt nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent tartaric acid and EDTA (0.02 mol each) after complete dissolution, adding 2.0mmol of cobalt fluoride, stirring for 6h, performing hydrothermal reaction at 160 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 2.0mmol of fluorine ion doped LaCoO under the conditions of heating rate of 5 ℃/min and calcining at 900 ℃ for 2h 3 . LaCoO is carried out 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaCoO 3 -2.0mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 。WHSV＝60000mL·g -1 ·h -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in Table 1As shown.
Example 7
Firstly, adding 0.005mol of lanthanum nitrate and 0.004mol of ferric nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent tartaric acid after complete dissolution, adding 1.0mmol of ferric fluoride, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 200 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 1.0mmol of fluoride ion doped LaFeO under the conditions of heating rate of 10 ℃/min and calcining at 1000 ℃ for 2h 3 . LaFeO is prepared 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaFeO 3 -1.0mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 8
Firstly, adding 0.005mol of lanthanum nitrate and 0.0035mol of ferric nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent EDTA after complete dissolution, adding 1.5mmol of ferric fluoride, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 170 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and calcining at 900 ℃ for 2h at a heating rate of 10 ℃/min to prepare 1.5mmol of fluoride ion doped LaFeO 3 . LaFeO is prepared 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaFeO 3 -1.5mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Example 9
Firstly, adding 0.005mol of lanthanum nitrate and 0.003mol of ferric nitrate into a beaker; then add 20Dissolving mL of deionized water, adding 0.04mol of complexing agent tartaric acid and citric acid (0.02 mol each) after complete dissolution, adding 2.0mmol of ferric fluoride, stirring for 6h, performing hydrothermal reaction at 190 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and preparing 2.0mmol of fluorine ion doped LaFeO under the conditions of heating rate of 10 ℃/min and calcining at 900 ℃ for 2h 3 . LaFeO is prepared 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaFeO 3 -2.0mmolF, then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Comparative example 1 preparation of LaMnO undoped with fluoride 3
Adding 0.005mol of lanthanum nitrate and 0.005mol of manganese nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent citric acid and EDTA (0.02 mol each) after complete dissolution, stirring for 6h, performing hydrothermal reaction at 160 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and calcining at 900 ℃ for 2h at a heating rate of 2 ℃/min to prepare the non-fluoride-ion-doped LaMnO 3 The method comprises the steps of carrying out a first treatment on the surface of the LaMnO is added to 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaMnO 3 Then, the catalytic combustion performance of the toluene is evaluated, and the evaluation conditions are as follows: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Comparative example 2 preparation of LaCoO undoped with fluoride 3
Adding 0.005mol of lanthanum nitrate and 0.005mol of cobalt nitrate into a beaker; then adding 20mL of deionized water for dissolution, and after complete dissolution, adding 0.04mol of complexing agent tartaric acid and EDTA (each0.02 mol), stirring for 6h, performing hydrothermal reaction at 170 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and calcining at a heating rate of 5 ℃/min and 900 ℃ for 2h to prepare the LaCoO without doping fluoride ions 3 The method comprises the steps of carrying out a first treatment on the surface of the LaCoO is carried out 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaCoO 3 Then, the catalytic combustion performance of the toluene is evaluated, and the evaluation conditions are as follows: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Comparative example 3 preparation of LaFeO undoped with fluoride 3
Adding 0.005mol of lanthanum nitrate and 0.005mol of ferric nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent EDTA after complete dissolution, stirring for 6h, performing hydrothermal reaction at 180 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and calcining at the temperature rising rate of 10 ℃/min and 900 ℃ for 2h to prepare the LaFeO without doping fluoride ions 3 The method comprises the steps of carrying out a first treatment on the surface of the LaFeO is prepared 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaFeO 3 Then, the catalytic combustion performance of the toluene is evaluated, and the evaluation conditions are as follows: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Comparative example 4
Adding 0.005mol of lanthanum nitrate and 0.003mol of cobalt nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent citric acid after complete dissolution, adding 2.0mmol of cobalt chloride, stirring for 6h, performing hydrothermal reaction at 180 ℃ in a reaction kettle for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and heating at a rate of 2 DEG CPreparation of 2.0mmol chloride doped LaCoO at 900 ℃ for 2h in per min 3 The method comprises the steps of carrying out a first treatment on the surface of the LaCoO is carried out 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaCoO 3 -2.0mmolCl, and then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Comparative example 5
Adding 0.005mol of lanthanum nitrate and 0.003mol of cobalt nitrate into a beaker; adding 20mL of deionized water for dissolution, adding 0.04mol of complexing agent EDTA after complete dissolution, adding 2.0mmol of cobalt bromide, stirring for 6h, performing hydrothermal reaction in a reaction kettle at 180 ℃ for 10h, drying a sample in the reaction kettle at 80 ℃ overnight to obtain a catalyst precursor, placing the catalyst precursor in a muffle furnace, and calcining at 900 ℃ for 2h at a heating rate of 2 ℃/min to prepare 2.0mmol bromide doped LaCoO 3 The method comprises the steps of carrying out a first treatment on the surface of the LaCoO is carried out 3 Tabletting the powder, grinding the powder into particles with 40 to 60 meshes, and marking the obtained catalyst as LaCoO 3 -2.0mmolBr, and then the catalytic combustion performance of toluene was evaluated under the following conditions: 100mg of catalyst is filled into a reactor, the toluene concentration is 1000ppm, the synthetic air is balance gas, and the flow is 100 mL-min -1 ，WHSV＝60000mL·g -1 ·h -1 . The toluene catalytic combustion effect of the catalyst is shown in table 1.
Table 1 toluene catalytic combustion performance of catalyst
As can be seen from Table 1, the catalytic oxidation performance of VOCs of the perovskite oxide catalyst doped with fluorine ions is remarkably improved,in the activity evaluation of the catalyst provided by the invention, the catalytic activity is greatly improved, T 90 (the temperature at which the conversion is 90%) is reduced by at most 60℃compared to the untreated catalyst. It can also be seen from example 9 and comparative examples 4-5 that the catalytic oxidation performance of VOCs of the perovskite-type oxide catalyst after doping with fluoride ions is also significantly higher than that of perovskite-type oxide catalysts after doping with chlorine and bromine ions. LaMnO before and after doping by fluoride ions in the embodiment of the invention 3 The comparison of the catalytic performance is shown in FIG. 1, and it can be seen from FIG. 1 that LaMnO doped with fluorine ions 3 The catalytic oxidation performance of the VOCs of the catalyst is obviously higher than that of the catalyst without doping fluoride ions, and with the increase of the doping amount of the fluoride ions, T 90 (the conversion rate is 90%) and the catalytic oxidation performance is improved.
In the embodiment of the invention, laCoO is doped before and after fluorine ions 3 The comparison of the catalytic performance is shown in FIG. 2, and it can be seen from FIG. 2 that LaCoO doped with fluorine ions 3 The catalytic oxidation performance of the VOCs of the catalyst is obviously higher than that of the catalyst without doping fluoride ions, but when the doping amount of the fluoride ions is increased to 2.5mmol, T 90 (the conversion rate is 90% of the temperature) and a small increase starts to appear, which shows that the doping amount of the fluoride ions is not as high as the doping amount, and is optimal in 1.0-2.0 mmol;
in the embodiment of the invention, laFeO is doped before and after fluorine ions 3 The comparison of the catalytic performance of (C) is shown in FIG. 3, and as can be seen from FIG. 3, laFeO doped with fluorine ions 3 The catalytic oxidation performance of the VOCs of the catalyst is obviously higher than that of the catalyst without doping fluoride ions, the doping amount of the fluoride ions is in the range of 1.0-2.5mmol, and T 90 (temperature at which conversion was 90%) was not significant, and when the fluorine ion doping amount was increased to 2.5mmol, T was not significant 90 (at a temperature of 90% conversion) also starts to increase slightly, indicating that the doping level of fluoride ions is not as high as better, optimally in the range of 1.0-2.0 mmol;
comparative example chloride and Bromide doped LaCoO 3 The catalytic performance is shown in FIG. 4, and it can be seen from FIG. 4 that VOCs of perovskite oxide catalyst doped with chloride ions and bromide ionsThe catalytic oxidation performance difference is not obvious, but is not obvious like that of perovskite oxide catalysts doped with fluoride ions.
2.0mmolF doped LaCoO prepared in example 6 of the present invention 3 The stability of the toluene degradation performance of the catalyst is shown in figure 5, and the toluene degradation performance of the F-doped perovskite type oxide is shown as unchanged in figure 5 within 50 hours, which shows that the catalyst has excellent toluene degradation stability.
The above additional technical features can be freely combined and superimposed by a person skilled in the art without conflict.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (5)
1. The application of a perovskite oxide catalyst in catalyzing the combustion of VOCs is characterized in that the catalyst is prepared by a method for activating lattice oxygen on the surface of the perovskite oxide, and the method comprises the following steps:
s1, firstly mixing lanthanum nitrate and nitrate, adding water for dissolution, adding a complexing agent after complete dissolution, and finally adding fluoride salt, and stirring, wherein the addition amount of the fluoride salt is 10% -50% of that of lanthanum nitrate substances;
s2, carrying out hydrothermal reaction on the stirred solution in the step S1, and drying overnight after the hydrothermal reaction is finished to obtain a catalyst precursor, wherein the hydrothermal reaction temperature is 160-200 ℃ and the hydrothermal reaction time is 10 hours;
s3, calcining the catalyst precursor obtained in the S2;
the fluoride salt is cobalt fluoride, ferric fluoride or manganese fluoride.
2. The use of the perovskite oxide catalyst according to claim 1 for catalyzing the combustion of VOCs, wherein the nitrate is cobalt nitrate, iron nitrate or manganese nitrate.
3. The use of the perovskite oxide catalyst according to claim 1 for catalyzing the combustion of VOCs, wherein the complexing agent is one or more of tartaric acid, citric acid and EDTA.
4. The use of the perovskite oxide catalyst according to claim 1 for catalyzing the combustion of VOCs, wherein the calcination temperature is 700-1000 ℃ and the calcination time is 2 hours.
5. Use of the perovskite oxide catalyst according to claim 1 for catalyzing the combustion of VOCs, wherein the calcination process has a temperature rise rate of 2-10 ℃/min.
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